TW200301263A

TW200301263A - Acrylic resin and antifouling coating

Info

Publication number: TW200301263A
Application number: TW091137244A
Authority: TW
Inventors: Naoki Yamamori; Kiyoaki Higo; Masayuki Matsuda
Original assignee: Nippon Paint Co Ltd; Nippon Paint Marine Coatings Co Ltd
Priority date: 2001-12-26
Filing date: 2002-12-25
Publication date: 2003-07-01
Also published as: EP1323745B1; EP1323745A2; CN1250586C; NO339571B1; CN1432585A; US20030139558A1; SG123546A1; TWI290148B; JP3958681B2; NO328137B1; KR100975322B1; DE60207968T2; KR20030055157A; DK1323745T3; EP1323745A3; NO20083930L; NO20026203L; AU2002325481B2; DE60207968D1; JP2003252931A

Abstract

The present invention has for its object to provide an antifouling coating improved in such a manner that the coating film formed therefrom may retain a steady polishing rate over a long time period and be not ready to develop cracks and other defects, thus exhibiting a excellent long-term antifouling performance. An acrylic resin having at least one group represented by the following general formula (1): (wherein R1, R2 and R3 may be the same or different and each represents a hydrocarbon residue of 1 to 20 carbon atoms) in its side chain and additionally at least one group represented by the following general formula (2): (wherein X is a group represented by the formula: n is equal to 0 or 1; Y represents a hydrocarbon; M represents a divalent metal; and A represents a monobasic organic acid residue)in its side chain.

Description

玖、發明說明發明領域本發明關於丙烯酸樹脂及含其之防污塗料。先前技術船、魚網及其它水下構造係易於吸引海洋生物如藤壺、殼菜及海藻，因此例如防礙船之有效率的航行及使遭受困擾如燃料的浪費，或阻塞魚網而縮短使用壽命。爲了防止生物黏附於如此的水下構造，通常於水下構造的表面塗佈防污塗料。在各種防污塗料中，近來廣泛使用可水解性防污塗料，因爲其具有能長時間維持防污性能的優良。最近，已經開發出含有含三有機矽烷基的樹脂之塗料（日本專利公開平-146808、日本專利公開平-31372、日本專利公開平-264170 、曰本專利公開平-07-102193等）。然而，由含有含三有機矽烷基的樹脂之塗料所可得到的塗膜通常易於發生裂紋或剝離而且具有太快的溶解速率。曰本專利公開2001-226440揭示一種塗料組成物，其包括一含（甲基）丙烯酸三異丙基矽烷酯、丙烯酸甲氧基乙酯及其它可聚合性單體及防污劑。此組成物的理論基礎在於：經由使用特定的（甲基）丙烯酸三有機矽烷酯，吾人可能找到擱置壽命的改良及5崔保即使由所儲存的塗料來形成塗膜仍能具有所需要的撓性及長期防污性能。另一方面，現今所用之含有三有機矽烷基的任何塗料之缺點爲：由其所形成的塗膜在某一期間中通常會溶出而 200301263 喪失其的防污性能，因此需要重塗以再現所必須的防污性能。爲了排除該困擾，最好能延長塗膜的使用壽命，因此對於較長作用的防污塗料係有大的需求。爲了能提供該具有較長作用的防污塗料，合理的措施似乎爲改良塗膜的特性，方式爲使得其在水中能長時間保持固定的拋光速率且較不易發生裂紋和其它缺陷。發明槪述鑒於上述的現今技術狀態，本發明之目的爲提供一種防污塗料，其經改良以·便由其所形成的塗膜可長時間保持穩定的拋光速率而且不易發生裂紋和其它缺陷，因此表現優良的長期防污性能。本發明關於一種丙烯酸樹脂，其具有至少一個由以下通式（1)所表示的基： Ο R1 ——C—0—Si—R2 (1) (其中R1、R2和R3係相同或不同且各代表1至20個碳原子的烴殘基）在其側鏈中且更具有至少一個由以下通式（2)所表示的基： 0 (2)(Ii) Description of the invention Field of the invention The present invention relates to an acrylic resin and an antifouling paint containing the same. Prior art boats, fishnets and other underwater structures are prone to attract marine life such as barnacles, shell vegetables and seaweeds, thus preventing, for example, the efficient navigation of the ship and causing problems such as waste of fuel, or shortening the service life of the fishnets . To prevent organisms from adhering to such underwater structures, antifouling coatings are usually applied to the surface of underwater structures. Among various antifouling coatings, a hydrolyzable antifouling coating has recently been widely used because it has an excellent ability to maintain antifouling performance for a long time. Recently, coatings containing a triorganosilyl-containing resin have been developed (Japanese Patent Publication No. Hei-146808, Japanese Patent Publication Hei-31372, Japanese Patent Publication Hei-264170, Japanese Patent Publication Hei-07-102193, etc.). However, the coating film obtainable from a coating containing a triorganosilyl-containing resin is generally susceptible to cracking or peeling and has a too fast dissolution rate. Japanese Patent Publication 2001-226440 discloses a coating composition comprising a triisopropylsilyl (meth) acrylate, methoxyethyl acrylate, and other polymerizable monomers and an antifouling agent. The theoretical basis of this composition is: Through the use of specific (meth) acrylic acid triorganosilyl esters, we may find improvements in shelf life and 5 Cui Bao Even if the coating film is formed from the stored coating, it can still have the required flexibility And long-term antifouling performance. On the other hand, the disadvantage of any coating containing triorganosilyl used today is that the coating film formed from it usually dissolves in a certain period and 200301263 loses its antifouling performance, so it needs to be re-coated to reproduce the Required antifouling performance. In order to eliminate this problem, it is better to extend the service life of the coating film, so there is a great demand for a long-acting antifouling coating system. In order to be able to provide this antifouling coating with longer effects, reasonable measures seem to be to improve the characteristics of the coating film in such a way that it can maintain a fixed polishing rate in water for a long time and is less prone to cracks and other defects. SUMMARY OF THE INVENTION In view of the current state of the art, the object of the present invention is to provide an antifouling coating which is improved so that the coating film formed by it can maintain a stable polishing rate for a long time and is less prone to cracks and other defects. Therefore, it exhibits excellent long-term antifouling performance. The present invention relates to an acrylic resin having at least one group represented by the following general formula (1): 〇 R1 ——C-0-Si-R2 (1) (wherein R1, R2 and R3 are the same or different and each A hydrocarbon residue representing 1 to 20 carbon atoms) in its side chain and further has at least one group represented by the following general formula (2): 0 (2)

—(X)—C—ο—Μ—A 200301263 (其中X係由下式所表示的基： 0— (X) —C—ο—Μ—A 200301263 (where X is a group represented by: 0

II —0——C—γ— η等於0或1 ; Υ代表烴殘基；Μ代表二價金屬；而Α代表一元有機酸殘基）在其側鏈中。本發明更關於一種丙烯酸樹脂，其可由以下步驟來獲得： (A)步驟，包括聚合3至50重量％的可聚合性不飽和有機酸、90至5重量％以下通式（3)所表示的（甲基）丙烯酸三有機矽烷酯： Z 0 R4 H2C=C—C—〇—Si—R5 (3) (其中Z代表氫原子或甲基；R4、R5和R6係相同或不同且各代表1至20個碳原子的烴殘基）和一或多種其它可共聚合性不飽和單體，及 (B)步驟，其包括使上述步驟（A)所獲得的樹脂、金屬化合物和一元酸進行反應。剛剛所提及的一元酸較佳爲一元環狀有機酸。 2〇〇3〇i£63 較宜地，該一元酸係至少一員選自由松香、氫化松香 '歧化松香、環烷酸、松香酸、氫化松香酸及去氫松香酸所組成族群者。在以上通式（1)中，R1、R2和R3較佳各爲異丙基。在以上通式（3)中，R4、R5和R6較佳各爲異丙基。本發明更關於一種含有上述定義的丙烯酸樹脂之防污塗料。現在詳細說明本發明。發J月的詳細說明依本發明第一觀點的丙烯酸樹脂係具有至少一個以上通式（1)所表示的基在樹脂的側鏈中且具有至少一個以上通式（2)所表示的基。然而，由含有僅具有三有機矽烷基的樹脂之防污塗料所形成的塗膜在某一期間會溶出而造成困擾，如較早喪失防污性能，依本發明的丙烯酸樹脂不僅含有至少一個以上通式（1)所表示的基而且含有至少一個以上通式（2)所表示的基，其沒有該些缺點。因此，由含有本發明丙烯酸樹酯的防污塗料所可獲得的塗膜係在水中能長時間保持穩定的拋光速率而且表現優良的長期防污性能。因此，不像由含有本發明丙烯酸樹脂的塗料所可獲得 .的塗膜，由含有僅具有以上通式（1)所表示的基在側鏈中的樹脂之塗料及僅具有三烷基矽烷基的樹脂所可獲得的塗膜係不能在水中足夠長時間地保持穩定的拋光速率。換言之，由含有本發明丙烯酸樹脂的防污塗料所可獲得的塗膜係能提供一種效果，其不能容易地由只含有僅具有以上通式 12 2 u Ο 3 01 £ 6 3 (1)所表示的基之樹脂和僅具有三烷基矽烷基的樹脂之摻合物的防污塗料獲得。在以上通式（1)中，R1、R2和R3係相同或不同且各代表 1至20個碳原子的烴殘基，例如直鍵或支鏈烷基，如甲基、乙基、丙基、異丙基、正丁基、異丁基、第二丁基、第二丁基、戊基、己基、庚基、辛基、壬基、癸基--基、十二基、十三基、十四基等；環狀烷基如環己基、經取代的環己基等；及芳基和經取代的芳基。作爲上述之經取代的芳基，可提及之經取代的芳基爲經鹵素、最高約18個碳原子的烷基、醯基、硝基、胺基或類似基所取代者。這些中，異丙基係較佳的，因爲其提供穩定的拋光速率和長期穩定的防污性能。更佳地，在以上通式（1)中，R1、R2和R3皆代表異丙基。在此情況中，塗膜表現更穩定的拋光速率及長期穩定的防污性能。在以上通式（2)中，Μ代表二價金屬，其不僅包括（但不限於）元素週期表第3Α_7Α、8和1Β-7Β族之元素。在這些中，銅和鋅係較佳的。在該丙烯酸樹脂的不揮發性成分中，上述二價金屬（Μ) 的比例較佳爲最小0.3重量％且最大20重量％，樹脂中金屬鹽成分的水解僅產生非常慢的溶析速率。另一方面，若其超過20重量％，則塗膜溶析速率將太快。因此，兩種情況皆不可接受的。更佳的比例爲最小0.5重量％且最大15重量％。 13 再者，在以上通式（2)中，A代表一元有機酸殘基，且此一元酸例如可爲一元環狀有機酸。剛剛所提及的一元環狀有機酸係沒有特別的限制，但是包括含環烷基的酸，如環烷酸，及樹脂酸如三環樹脂酸，包含其鹽。剛剛所提及的三環樹脂酸係沒有特別的限制，但是包括具有二類結烴骨架的一元酸。因此例如，可提及者爲具有松香烷、右松脂烷、異右松脂烷或香茶烷核；特定的松香酸、新松香酸、去氫松香酸、氫化松香酸、巴拉史特利可（parastdc)酸、海松酸、異海松酸、左旋海松酸、右旋海松酸及山達拉海松酸等。這些中，松香酸及氫化松香酸（含其鹽）係部分較佳的，因爲可進行適當的水解以提供所獲得的塗膜之優良的長期防污性及高的抗龜裂性，及部分由可用性之觀點而言。上述一兀環狀有機酸不需要已被高度純化，但是例如可採用松樹松香、松樹香茅酸等。作爲具體例子，可提及者爲氫化松香及妥爾油松香等。松香、氫化松香及歧化松香係較佳的，因爲它們不僅可容易以低成本取得及容易處理而且有助於長期防污性能。可各自獨立地或組合二或多種來使用這些一元環狀有機酸。在本發明之實施中可用的一元酸中，該一元環狀有機酸以外者係含1至20個碳原子的一元酸，如乙酸、丙酸、丁酸、月桂酸、硬脂酸、亞麻油酸、油酸、氯乙酸、氟乙酸、戊酸等。可各自獨立地或組合二或多種來使用這些一 20030Π63 元酸。在以上通式（2)中所定義的一元有機酸殘基中，該環狀有機酸較佳爲佔最小5莫耳％及最大1〇〇莫耳％。更佳的比例爲15莫耳％至100莫耳％，尤更佳的比例爲25莫耳％至 100莫耳％。若其少於5莫耳％，則塗膜的長期防污性能及抗龜裂性可能不滿足。用於導入該一元環狀有機酸殘基的一元環狀有機酸之酸値係最小100mg ΚΟΗ/g且最大220mg ΚΟΗ/g，較佳爲最小120mg ΚΟΗ/g且最大190mg KOH/g。在此範圍內，丙烯酸樹脂的水解係以適當的速率進行，俾可保持穩定的拋光速率以確保延長時間的長期防污性能。尤更佳的範圍爲最小 140mg ΚΟΗ/g 且最大 185mg ΚΟΗ/g。再者，在以上通式（2)中，Y係沒有特別的限制，只要其爲烴殘基。例如，殘基可爲在添加二元酸如苯二甲酸、琥珀酸、馬來酸或類似酸至可聚合性不飽和有機酸單體而獲得者。因此，可藉由將二元酸加到不飽和一元酸羥基烷酯及將它們共聚合以產生一種樹脂或替代地使該二元酸存在於樹脂製造系統中或在其製造後而導入Υ。在此情況中，η=1 0 依本發明第二觀點的丙烯酸樹脂係由一種方法而獲得者，該方法包括：（A)第一步驟，其包括聚合3至50重量％的可聚合性不飽和有機酸、90至5重量％以上通式（3)所表示的（甲基）丙烯酸三有機矽烷酯及一或多種其它可共聚合性不飽和單體；及（B)第二步驟，其包括使該第一步驟所獲得 15 200301263 的樹脂、金屬化合物和一元酸進行反應。上述第一步驟係步驟（A)，其中3至50重量％的可聚合性不飽和有機酸、90至5重量％以上通式（3)所表示的（甲基 )丙烯酸三有機矽烷酯及一或多種其它可共聚合性不飽和單體係被共聚合。上述可聚合性不飽和有機酸係沒有特別的限制，但是包括具有至少一個羧基的有機酸。作爲該酸，可提及者爲不飽和一元酸，如（甲基）丙烯酸等；不飽和二元酸，包含其之單烷基醚，如馬來酸及其單烷基醚、伊康酸及其單烷基醚等；二元酸對不飽和一元酸羥基烷基酯的加成物，如（甲基）丙烯酸2-羥基乙酯-苯二甲酸加成物、（甲基）丙烯酸2-羥基乙酯-琥珀酸加成物等等。可各自獨立地或組合二或多種來使用這些可聚合性不飽和有機酸。以100重量％用於第一步驟之聚合反應的全部單體成分爲基準，上述可聚合性不飽和有機酸的比例應爲最小3重量％且最大50重量％。若該比例少於3重量％，則塗膜的柔軟性和撓性傾向於變差。若其超過50重量％，則防污性能可能不能維持足夠長的時間。在上述通式（3)所表示的（甲基）丙烯酸三有機矽烷酯中，Z代表氫原子或甲基。 R4、R5和R6可爲相同或不同且各代表含1至20個碳原子的烴殘基，其包括相同於上述爲R1、R2和R3所述的烴殘基。通式（3)中的R4、R5和R6更佳爲皆是異丙基。在此情 16 況中’塗膜的拋光速率變得更穩定以確保長期穩定的防污性能。以上通式（3)所表示的（甲基）丙烯酸三有機矽烷酯係沒有特別的限制，但是包括（甲基）丙烯酸三甲基矽烷酯、（甲基）丙烯酸三乙基矽烷酯、（甲基）丙烯酸三正丙基矽烷酯、（甲基）丙烯酸三異丙基矽烷酯、（甲基）丙烯酸三正丁基矽烷酯、（甲基）丙烯酸異正丁基矽烷酯、（甲基）丙烯酸三第二丁基矽烷酯、（甲基）丙烯酸正戊基矽烷酯、（甲基）丙烯酸正己基矽烷酯、（曱基）丙烯酸三正辛基矽烷酯、（甲基）丙烯酸三正十二基矽烷酯、（甲基）丙烯酸三苯基矽烷酯、（甲基）丙烯酸對甲基苯基矽烷酯、及（甲基）丙烯酸三苄基矽烷酯等等。作爲以上通式（3)所表示的（甲基）丙烯酸三有機矽烷酯之其它例子，可提及者爲（甲基）丙烯酸乙基二甲基矽烷酯、 (甲基）丙烯酸正丁基二甲基矽烷酯、（甲基）丙烯酸二異丙基正丁基二甲基矽烷酯、（甲基）丙烯酸二異丙基硬脂醯基矽烷酯、（甲基）丙烯酸二環己基苯基矽烷酯、（甲基）丙烯酸第三丁基二苯基矽烷酯、（甲基）丙烯酸月桂二苯基矽烷酯、及（甲基）丙烯酸第三丁基間硝基苯基甲基矽烷酯等等。在這些中，從長期穩定的拋光速率的觀點而言，（甲基）丙烯酸三異丙基矽烷酯係較佳的。可各自獨立地或組合二或多種來使用這些（甲基）丙烯酸三有機矽烷酯。以100重量％用於第一步驟之聚合反應的全部單體成分爲基準，依以上通式（3)的（甲基）丙烯酸三有機矽烷酯的比例應爲最大90重量％且最小5重量％。若其超過90重量％ 17 200301E63 ，則塗膜將易於剝離。若其少於5重量％，則三有機矽烷基在樹脂的比例將太小而不能確保長期防污性能。較佳的比例爲最大7 0重量％且最小1 〇重量％。上述其它可共聚合性不飽和單體係沒有特別的限制，但是包括在酯部分含有1至20碳原子的（甲基）丙烯酸烷酯，如（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基 )丙烯酸第三丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂醯酯等；在酯部分含有1至 20碳原子的含羥基之（甲基）丙烯酸烷酯，如（甲基）丙烯酸2 羥基丙酯、（甲基）丙烯酸2-羥基乙酯等；（甲基）丙烯酸環狀烴酯，如（甲基）丙烯酸苯酯、（甲基）丙烯酸環己酯等；（甲基 )丙烯酸的聚伸烷二醇酯，如單（甲基）丙烯酸聚乙二醇酯、單（甲基）丙烯酸的聚乙二醇（聚合度爲：2至10)酯等；（甲基 )丙烯酸CV3烷氧基烷酯、（甲基）丙烯醯胺；乙烯系化合物，如苯乙烯、α-甲基苯乙烯、醋酸乙烯酯、丙酸乙烯酯、苯甲酸乙烯酯、乙烯基甲苯、丙烯腈等；巴豆酸酯；不飽和二元酸二酯，如馬來酸二酯、伊康酸二酯等。上述（甲基）丙烯酸酯的酯部分較佳爲含1-8個碳原子的烷基，更佳爲含1-20個碳原子的院基。較佳者爲（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯及（甲基）丙烯酸環己酯。可各自獨立地或組合二或多種來使用這些單體。該第一步驟中所用的聚合技術係沒有特別的限制，但是例如可包括使含該可聚合性不飽和有機酸、該（甲基）丙烯 18 20030 *、广，产、 -b j 酸三有機矽烷酯及該其它可共聚合性單體的單體成分混合聚合引發劑，如偶氮化合物或過氧化物，以製備一種混合物溶液，將它滴入溶劑如二甲苯、正丁醇或類似物中，及使它在加熱下反應。該第一步驟中所獲得的樹脂之數量平均分子量係沒有特別的限制，但是較佳爲最小2,000且最大100,000，更佳 3,000至40,000。若其少於2,〇〇〇，則塗膜形成性係傾向於不足的。若其ώ過100,000，則可獲得的塗料將不僅無法具有實用的擱置壽命而且從公共衛生及經濟的觀點看係令人不滿意的，因此在現場將需要大量的溶劑來稀釋。該第一步驟中所獲得的樹脂具有30至300mg KOH/g的酸値。若其少於30，則附著於側鏈的金屬鹽量將太少而不能產生足夠的防污性能。若其超過300，則溶析速率將太高而不能提供長期防污性能。上述第二步驟係一種步驟，其中該第一步驟中所獲得的樹脂、金屬化合物及一元酸係一起反應。因此，此第二步驟中所可獲得的丙烯酸樹脂係具有至少一種由以上通式 (2)所表示的側鏈。上述的金屬化合物係沒有特別的限制，但是包括金屬的氧化物、氫氧化物、氯化物、硫化物及驗式碳酸鹽。可各自獨立地或組合二或多種來使用這些金屬化合物。上述的一元酸係沒有特別的限制；因此其包括（但不限於）上述所提及的酸。在此第二步驟中使第一步驟中所獲得的樹脂與該金屬 19 1263 化合物和一元酸反應之方法可爲習知者，但是較佳爲在溫度低於金屬酯的分解溫度進行程序如加熱和攪拌。本發明的丙烯酸樹脂不僅可由上述方法而且可由以下和其它方法來獲得。 (1)方法，其中將由可聚合性不飽和有機酸、上述通式（3)的( 甲基）丙烯酸三有機矽烷酯和其它可共聚合性不飽和單體之反應所獲得的樹脂與一元酸金屬鹽反應，或⑵方法，其包括使可聚合性不飽和有機酸與金屬化合物和一元酸反應或與一元酸金屬鹽反應，及使所產生的含金屬不飽和單體與上述通式（3)的（甲基）丙烯酸三有機矽烷酯和其它可共聚合性不飽和單體進行聚合。因爲上述技術所可獲得的丙烯酸樹脂係具有至少一個單元，各側鏈衍生自上述通式（3)的（甲基）丙烯酸三有機矽烷酯和上述通式（2)所表示的側鏈，因此其不僅沒有塗膜在有限期間內會溶出的缺陷（如含有含三有機矽烷基的樹脂之習用防污塗料者）而且確保穩定的拋光速率，不會發生塗膜龜裂，因此提供長期優良的防污性能。可用習知的添加劑，包括防污劑，來補充上述方式所獲得的丙烯酸樹脂，以製備一種防污塗料。所產生的防污塗料係一種自動拋光可水解性防污塗料。爲了調整塗膜的物理特性和消耗速率，依本發明的防污塗料除了含有該丙烯酸樹脂亦可含有一或多種其它黏結劑樹脂。該其它黏結劑樹脂的調整重量比係較佳爲[丙烯酸樹脂]:[其它黏結劑樹脂]= 100:0〜50:50，此係以不揮發性成 20030Π63 分爲基準。若該其它黏結劑樹脂的比例超過上述範圍，則塗膜的長期優良防污性能和足夠的抗龜裂性可能不能令人滿意地和諧一致。作爲該其它黏結劑樹脂，可提及者爲氯化石蠘、聚（乙烯醚）、聚（癸二酸伸丙酯）、部分氫化的聯三苯、聚（醋酸乙 .烯酯）、聚（甲基）丙烯酸烷酯、聚醚多元醇、醇酸樹脂、聚酯樹脂、聚（氯乙烯）、聚矽氧油、蠟、白石蠟脂、液體石蠟、松香、氫化松香、環烷酸，及脂肪酸和其二價金屬鹽等〇可用習知的添加劑如防污劑、塑化劑、顏料、溶劑等來補充上述防污塗料。上述防污劑係沒有特別的限制，但是可採用已知的物質。例如可提及無機化合物、含金屬的有機化合物、無金屬的有機化合物等。具體地，防污劑包括（但不限於）氧化低價銅、伸乙基雙 (二硫胺甲酸）鎂、二甲基胺甲酸鋅、2-甲基硫基-4-第三丁基胺基-6-環丙基胺基+三啡、2,4,6-四氯異肽腈、N，N-二甲基二氯苯基脲、伸乙基雙（二硫胺甲酸）鋅、硫氰化銅、4,5-二氯-2-正辛基-3(2H)-異噻唑酮、N-(氟二氯甲基硫基）酞醯亞胺、N，N5-二甲基-Ν’-苯基（N-氟二氯甲基硫基）磺醯胺、2-毗陡硫醇-1-氧化物f羊鹽及銅鹽、一硫化四甲基氛荒醯、2,4,6_ 三氯苯基馬來醯亞胺、2,3,5,6-四氯-4-(甲基磺醯基）毗啶、 3-碘-2-丙基丁基胺甲酸酯、碘甲基對三硼、二氯化苯基（雙吡啶基）鉍、2-(4-噻唑基）苯並咪唑、三苯基硼毗啶鹽、硬脂 21 030Π63 醯胺-三苯基硼、及月桂胺-三苯基硼。可各自獨立地或組合二或多種來使用這些防污劑。以不揮發性成分爲基準，塗料中該防污劑的用量較佳爲最小0.1重量％且最大80重量％。若其少於0.1重量％，則不能預期目標的防污性能。若其超過80重量％，則塗膜傾向於發生缺陷如裂紋及剝離。更佳的用量爲最小1重量％且最大60重量％。II — 0 — C — γ — η is equal to 0 or 1; Υ represents a hydrocarbon residue; M represents a divalent metal; and A represents a monovalent organic acid residue) in its side chain. The invention further relates to an acrylic resin, which can be obtained by the following steps: (A) Step, comprising polymerizing 3 to 50% by weight of a polymerizable unsaturated organic acid, 90 to 5% by weight represented by the following general formula (3) Triorganosilyl (meth) acrylate: Z 0 R4 H2C = C—C—〇—Si—R5 (3) (where Z represents a hydrogen atom or a methyl group; R4, R5, and R6 are the same or different and each represents 1 Hydrocarbon residues of up to 20 carbon atoms) and one or more other copolymerizable unsaturated monomers, and step (B), which comprises reacting the resin, metal compound and monobasic acid obtained in the above step (A) . The monobasic acid just mentioned is preferably a monovalent cyclic organic acid. 20000i £ 63 Preferably, at least one member of the monobasic acid system is selected from the group consisting of rosin, hydrogenated rosin 'disproportionated rosin, naphthenic acid, rosin acid, hydrogenated rosin acid, and dehydroabietic acid. In the above general formula (1), R1, R2, and R3 are each preferably an isopropyl group. In the above general formula (3), R4, R5, and R6 are each preferably an isopropyl group. The invention further relates to an antifouling paint containing an acrylic resin as defined above. The present invention will now be described in detail. Detailed description of the first month The acrylic resin according to the first aspect of the present invention has at least one group represented by the general formula (1) in the side chain of the resin and has at least one group represented by the general formula (2). However, a coating film formed of an antifouling paint containing a resin having only a triorganosilyl group will dissolve during a certain period of time and cause problems. For example, if the antifouling property is lost earlier, the acrylic resin according to the present invention not only contains at least one or more The group represented by the general formula (1) and containing at least one group represented by the general formula (2) does not have these disadvantages. Therefore, the coating film obtainable from the antifouling paint containing the acrylic resin of the present invention can maintain a stable polishing rate in water for a long time and exhibit excellent long-term antifouling performance. Therefore, unlike a coating film obtainable from a coating containing the acrylic resin of the present invention, a coating containing a resin having only a group in the side chain represented by the above general formula (1) and a trialkylsilyl group are not included. The coating film obtainable by the resin cannot maintain a stable polishing rate in water long enough. In other words, the coating film system obtainable by the antifouling paint containing the acrylic resin of the present invention can provide an effect which cannot be easily represented by only containing only the general formula 12 2 u Ο 3 01 £ 6 3 (1) An antifouling coating is obtained by blending a resin based on a resin and a resin having only a trialkylsilyl group. In the above general formula (1), R1, R2 and R3 are hydrocarbon residues which are the same or different and each represents 1 to 20 carbon atoms, such as a straight or branched alkyl group, such as methyl, ethyl, propyl , Isopropyl, n-butyl, isobutyl, second butyl, second butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl--yl, dodecyl, tridecyl , Tetradecyl, etc .; cyclic alkyl groups such as cyclohexyl, substituted cyclohexyl, etc .; and aryl and substituted aryl. As the substituted aryl group mentioned above, a substituted aryl group may be mentioned which is substituted with a halogen, an alkyl group of up to about 18 carbon atoms, a fluorenyl group, a nitro group, an amine group or the like. Among these, isopropyl is preferred because it provides stable polishing rate and long-term stable antifouling performance. More preferably, in the above general formula (1), R1, R2 and R3 all represent isopropyl. In this case, the coating film exhibits a more stable polishing rate and a long-term stable antifouling performance. In the above general formula (2), M represents a divalent metal, which includes (but is not limited to) elements of Groups 3A-7A, 8, and 1B-7B of the Periodic Table of Elements. Among these, copper and zinc are preferred. Among the non-volatile components of the acrylic resin, the proportion of the divalent metal (M) is preferably at least 0.3% by weight and at most 20% by weight, and the hydrolysis of the metal salt component in the resin produces only a very slow dissolution rate. On the other hand, if it exceeds 20% by weight, the coating film dissolution rate will be too fast. Therefore, neither case is acceptable. A more preferred ratio is a minimum of 0.5% by weight and a maximum of 15% by weight. 13 Furthermore, in the above general formula (2), A represents a monovalent organic acid residue, and the monobasic acid may be, for example, a monocyclic organic acid. The monovalent cyclic organic acid system just mentioned is not particularly limited, but includes a cycloalkyl-containing acid such as naphthenic acid, and a resin acid such as tricyclic resin acid, including salts thereof. The tricyclic resin acid system just mentioned is not particularly limited, but includes a monobasic acid having a second-class hydrocarbon-binding skeleton. Thus, for example, mention may be made of having abietane, dextran, isoproxane, or catechin cores; specific abietic acids, neo-rosin acids, dehydroabietic acids, hydrogenated abietic acids, balastric (Parastdc) acid, pimaric acid, isopimaric acid, l-pimaric acid, d-pimaric acid and Sandara pimaric acid. Among these, abietic acid and hydrogenated abietic acid (including their salts) are partly preferable because appropriate hydrolysis can be performed to provide excellent long-term antifouling properties and high crack resistance of the obtained coating film, and part In terms of usability. The aforementioned monocyclic organic acid need not be highly purified, but, for example, pine rosin, pine citronellic acid, and the like can be used. As specific examples, hydrogenated rosin and tall oil rosin can be mentioned. Rosin, hydrogenated rosin, and disproportionated rosin are preferred because they are not only easily available at low cost and easy to handle, but also contribute to long-term antifouling performance. These monocyclic organic acids may be used each independently or in combination of two or more. Among the monobasic acids usable in the practice of the present invention, the monocyclic acid other than the monobasic cyclic organic acid is a monobasic acid containing 1 to 20 carbon atoms, such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linseed oil Acids, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid, etc. These mono-20030III acid can be used independently or in combination of two or more. Among the monovalent organic acid residues defined in the above general formula (2), the cyclic organic acid preferably accounts for a minimum of 5 mole% and a maximum of 100 mole%. A more preferable ratio is 15 to 100 mol%, and a more preferable ratio is 25 to 100 mol%. If it is less than 5 mol%, the long-term antifouling performance and crack resistance of the coating film may not be satisfied. The acid hydrazone of the monocyclic organic acid used for introduction of the monocyclic organic acid residue is a minimum of 100 mg KOH / g and a maximum of 220 mg KOH / g, preferably a minimum of 120 mg KOH / g and a maximum of 190 mg KOH / g. Within this range, the hydrolysis of acrylic resin is performed at an appropriate rate, and a stable polishing rate can be maintained to ensure long-term antifouling performance for an extended period of time. A more preferred range is a minimum of 140 mg KOΗ / g and a maximum of 185 mg KOΗ / g. Furthermore, in the above general formula (2), the Y system is not particularly limited as long as it is a hydrocarbon residue. For example, the residue may be obtained by adding a diacid such as phthalic acid, succinic acid, maleic acid or the like to a polymerizable unsaturated organic acid monomer. Therefore, thorium can be introduced by adding a dibasic acid to an unsaturated monobasic hydroxyalkyl ester and copolymerizing them to produce a resin or alternatively, allowing the dibasic acid to exist in a resin manufacturing system or after its manufacture. In this case, η = 1 0 The acrylic resin according to the second aspect of the present invention is obtained by a method including: (A) a first step including polymerizing 3 to 50% by weight of a polymerizable polymer; A saturated organic acid, 90 to 5% by weight or more of a triorganosilyl (meth) acrylate represented by the general formula (3) and one or more other copolymerizable unsaturated monomers; and (B) a second step, which It includes reacting 15 200301263 obtained in this first step, a metal compound and a monobasic acid. The above-mentioned first step is step (A), wherein 3 to 50% by weight of a polymerizable unsaturated organic acid, 90 to 5% by weight or more of the triorganosilyl (meth) acrylate represented by the general formula (3), and One or more other copolymerizable unsaturated monosystems are copolymerized. The polymerizable unsaturated organic acid is not particularly limited, but includes organic acids having at least one carboxyl group. As the acid, mention may be made of unsaturated monobasic acids, such as (meth) acrylic acid, etc .; unsaturated dibasic acids, including monoalkyl ethers thereof, such as maleic acid and its monoalkyl ethers, and itaconic acid And its monoalkyl ethers; adducts of dibasic acids to unsaturated monobasic hydroxyalkyl esters, such as 2-hydroxyethyl (meth) acrylate-phthalic acid adducts, (meth) acrylic acid 2 -Hydroxyethyl ester-succinic acid adduct and the like. These polymerizable unsaturated organic acids may be used each independently or in combination of two or more. Based on 100% by weight of all monomer components used in the polymerization reaction in the first step, the proportion of the polymerizable unsaturated organic acid should be at least 3% by weight and at most 50% by weight. If the proportion is less than 3% by weight, the flexibility and flexibility of the coating film tends to deteriorate. If it exceeds 50% by weight, the antifouling performance may not be maintained for a sufficient time. In the triorganosilyl (meth) acrylate represented by the general formula (3), Z represents a hydrogen atom or a methyl group. R4, R5 and R6 may be the same or different and each represents a hydrocarbon residue containing 1 to 20 carbon atoms, which includes the same hydrocarbon residues as described above for R1, R2 and R3. R4, R5 and R6 in the general formula (3) are more preferably all isopropyl groups. In this case, the polishing rate of the coating film becomes more stable to ensure long-term stable antifouling performance. The triorganosilyl (meth) acrylate system represented by the above general formula (3) is not particularly limited, but includes trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, and (methyl) Propyl) tri-n-propylsilyl acrylate, tri-isopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, iso-n-butylsilyl (meth) acrylate, (meth) Tri-second butylsilyl acrylate, n-pentylsilyl (meth) acrylate, n-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-decyl (meth) acrylate Diylsilyl ester, triphenylsilyl (meth) acrylate, p-methylphenylsilyl (meth) acrylate, and tribenzylsilyl (meth) acrylate, and the like. As other examples of the triorganosilyl (meth) acrylate represented by the above general formula (3), mention may be made of ethyldimethylsilyl (meth) acrylate and n-butyldimethacrylate Methylsilyl ester, diisopropyl-n-butyldimethylsilyl (meth) acrylate, diisopropylstearylmethylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate Ester, tert-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, and tert-butyl-m-phenylphenylsilyl (meth) acrylate, etc. . Among these, from the viewpoint of a long-term stable polishing rate, triisopropylsilyl (meth) acrylate is preferred. These triorganosilyl (meth) acrylates can be used independently or in combination of two or more of them. Based on 100% by weight of all monomer components used in the polymerization reaction of the first step, the proportion of the triorganosilyl (meth) acrylate according to the above general formula (3) should be a maximum of 90% by weight and a minimum of 5% by weight . If it exceeds 90% by weight 17 200301E63, the coating film will be easily peeled. If it is less than 5% by weight, the proportion of the triorganosilyl group in the resin will be too small to ensure long-term antifouling performance. A preferred ratio is a maximum of 70% by weight and a minimum of 10% by weight. The above other copolymerizable unsaturated monosystems are not particularly limited, but include alkyl (meth) acrylates containing 1 to 20 carbon atoms in the ester portion, such as (meth) acrylate, (meth) acrylic acid Ethyl ester, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Esters, lauryl (meth) acrylate, stearyl (meth) acrylate, etc .; hydroxyl-containing alkyl (meth) acrylates containing 1 to 20 carbon atoms in the ester portion, such as 2 hydroxy (meth) acrylate Propyl ester, 2-hydroxyethyl (meth) acrylate, etc .; Cyclic hydrocarbon esters of (meth) acrylic acid, such as phenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc .; Polyalkylene glycol esters, such as polyethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylic acid (degree of polymerization: 2 to 10), etc .; CV3 alkyl (meth) acrylate Oxyalkyl esters, (meth) acrylamidonium; vinyl compounds such as styrene, α-methyl Styrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl toluene, acrylonitrile, etc .; crotonic acid esters; unsaturated dibasic acid diesters, such as maleic acid diesters, itaconic acid diesters, etc. . The ester portion of the (meth) acrylate is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a radical having 1 to 20 carbon atoms. Preferred are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. These monomers can be used each independently or in combination of two or more. The polymerization technique used in the first step is not particularly limited, but may include, for example, the polymerizable unsaturated organic acid, the (meth) propylene 18 20030 *, KOHYAMA, -bj acid triorganosilane The ester and the monomer components of the other copolymerizable monomer are mixed with a polymerization initiator such as an azo compound or a peroxide to prepare a mixture solution, which is dropped into a solvent such as xylene, n-butanol, or the like , And make it react under heating. The number average molecular weight of the resin obtained in this first step is not particularly limited, but is preferably a minimum of 2,000 and a maximum of 100,000, and more preferably 3,000 to 40,000. If it is less than 2,000, the coating film forming property tends to be insufficient. If it is sold over 100,000, not only will the available coatings not have a practical shelf life, but it will also be unsatisfactory from a public health and economic point of view, so a large amount of solvent will be required to dilute on site. The resin obtained in this first step has an acid hydrazone of 30 to 300 mg KOH / g. If it is less than 30, the amount of metal salt attached to the side chain will be too small to produce sufficient antifouling performance. If it exceeds 300, the dissolution rate will be too high to provide long-term antifouling performance. The second step described above is a step in which the resin, metal compound and monobasic acid obtained in the first step are reacted together. Therefore, the acrylic resin system obtainable in this second step has at least one side chain represented by the above general formula (2). The above-mentioned metal compounds are not particularly limited, but include oxides, hydroxides, chlorides, sulfides, and carbonates of metals. These metal compounds may be used independently or in combination of two or more. The above-mentioned monobasic acid is not particularly limited; therefore, it includes (but is not limited to) the above-mentioned acids. In this second step, the method of reacting the resin obtained in the first step with the metal 19 1263 compound and a monobasic acid may be known, but it is preferable to perform a program such as heating at a temperature lower than the decomposition temperature of the metal ester. And stir. The acrylic resin of the present invention can be obtained not only by the above method but also by the following and other methods. (1) A method in which a resin obtained by a reaction of a polymerizable unsaturated organic acid, a triorganosilyl (meth) acrylate of the general formula (3), and other copolymerizable unsaturated monomers is reacted with a monobasic acid A metal salt reaction, or hydrazone method, comprising reacting a polymerizable unsaturated organic acid with a metal compound and a monoacid or with a monoacid metal salt, and reacting the generated metal-containing unsaturated monomer with the above general formula (3 ) (Trimethysilyl methacrylate) and other copolymerizable unsaturated monomers are polymerized. The acrylic resin obtainable by the above technique has at least one unit, and each side chain is derived from the triorganosilyl (meth) acrylate of the general formula (3) and the side chain represented by the general formula (2). Not only does it not have the defects that the coating film will dissolve in a limited period of time (such as those used in conventional antifouling coatings containing resins containing triorganosilyl groups), but also ensures a stable polishing rate without coating film cracking, so it provides excellent long-term Antifouling performance. The acrylic resin obtained in the above manner can be supplemented with conventional additives, including antifouling agents, to prepare an antifouling coating. The resulting antifouling paint is an automatically polished, hydrolyzable antifouling paint. In order to adjust the physical properties and consumption rate of the coating film, the antifouling paint according to the present invention may contain one or more other binder resins in addition to the acrylic resin. The adjusted weight ratio of the other binder resin is preferably [acrylic resin]: [other binder resin] = 100: 0 to 50:50, which is based on a nonvolatile component of 20030Π63. If the ratio of the other binder resin exceeds the above range, the long-term excellent antifouling performance and sufficient crack resistance of the coating film may not be satisfactorily harmonized. As the other binder resin, mention may be made of chlorinated arsenite, poly (vinyl ether), poly (propene sebacate), partially hydrogenated terphenyl, poly (ethylene vinyl acetate), poly ( Alkyl methacrylates, polyether polyols, alkyd resins, polyester resins, poly (vinyl chloride), silicone oils, waxes, white paraffin greases, liquid paraffin, rosin, hydrogenated rosin, naphthenic acid, and Fatty acids and their divalent metal salts and the like can be supplemented with conventional additives such as antifouling agents, plasticizers, pigments, solvents and the like. The antifouling agent is not particularly limited, but a known substance can be used. Mention may be made of, for example, inorganic compounds, metal-containing organic compounds, metal-free organic compounds, and the like. Specifically, the antifouling agent includes (but is not limited to) low-oxidized copper, magnesium bis (dithiocarbamate), zinc dimethylcarbamate, 2-methylthio-4-tert-butylamine -6-cyclopropylamino group + trimorphine, 2,4,6-tetrachloroisopeptidenitrile, N, N-dimethyldichlorophenylurea, zinc ethylbis (dithiocarbamate), Copper thiocyanide, 4,5-dichloro-2-n-octyl-3 (2H) -isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N5-dimethyl -N'-phenyl (N-fluorodichloromethylsulfanyl) sulfonamide, 2-pyridinethiol-1-oxide f sheep salt and copper salt, tetramethylammonium monosulfide, 2 ,, 4,6_ trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propylbutylcarbamate , Iodomethyl p-triboron, bis (phenylpyridyl) bischloride dichloride, 2- (4-thiazolyl) benzimidazole, triphenylboridinium salt, stearin 21 030Π63 hydrazine-triphenyl Boron, and laurylamine-triphenylboron. These antifouling agents may be used independently or in combination of two or more. Based on the non-volatile components, the amount of the antifouling agent in the coating is preferably at least 0.1% by weight and at most 80% by weight. If it is less than 0.1% by weight, the target antifouling performance cannot be expected. If it exceeds 80% by weight, the coating film tends to have defects such as cracks and peeling. A more preferred amount is a minimum of 1% by weight and a maximum of 60% by weight.

上述塑化劑包括肽酸酯塑化劑如肽酸二辛酯、畎酸二甲酯、酞酸二環己酯等；脂族二元酸酯塑化劑如己二酸異丁酯、癸二酸二丁酯等；二醇酯塑化劑如二乙二醇二苯甲酸酯、異戊四醇烷基酯等；磷酸酯塑化劑如二磷酸三氯乙烯酯、磷酸三氯乙酯等；環氧塑化劑如環氧化大豆油、環氧化硬脂酸辛酯等；有機錫塑化劑如月桂酸二辛錫、月桂酸二丁錫等；偏苯三甲酸三辛酯、甘油三醋酸酯等。可各自獨立地或組合二或多種來使用這些塑化劑。The above plasticizers include peptidate plasticizers such as dioctyl peptate, dimethyl gallate, dicyclohexyl phthalate, and the like; aliphatic plasticizers such as isobutyl adipate, decyl Dibutyl diacid, etc .; glycol ester plasticizers such as diethylene glycol dibenzoate, isopentaerythritol alkyl esters, etc .; phosphate ester plasticizers such as trichloroethylene diphosphate, trichloroethyl phosphate Esters; epoxy plasticizers such as epoxidized soybean oil and octyl stearate; organic tin plasticizers such as dioctyl tin laurate and dibutyl tin laurate; trioctyl trimellitate and glycerol Triacetate and so on. These plasticizers may be used independently or in combination of two or more.

上述顏料包括增量顏料，如沈澱鋇、滑石、黏土、白堊、矽石白、氧化鋁白、膨土等；及彩色顏料如二氧化鈦、氧化锆、鹼式硫酸鉛、氧化錫、碳黑、石墨、紅氧化鐵、鉻黃、肽青素綠、酞青素藍、喹吖啶酮等。可各自獨立地或組合二或多種來使用這些顏料。上述溶劑包括烴類，如甲苯、二甲苯、乙基苯、氯戊烷、辛烷、庚烷、環己烷、揮發油等；醚類，如二噁烷、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丁醚、乙二醇二丁醚、二乙二醇單甲醚、二乙二醇單乙醚等。 22 2ύϋ3〇1£63 酯類，如醋酸丁酯、醋酸丙酯、醋酸苄酯、乙二醇單甲醚醋酸酯、乙二醇單乙醚醋酸酯等；酮類，如乙基異丁基酮、甲基異丁基酮等；及醇類，如正丁醇、丙醇等等。可各自獨立地或組合二或多種來使用這些溶劑。就其它添加劑而言，並沒有特別的限制。例如，可提及者爲一元有機酸，如酞酸一丁酯、琥珀酸辛酯等，樟腦、蓖麻油等；水結合劑、防流淌劑、防溢流劑；防沈降劑 ;及消泡劑等等。依本發明的防污塗料例如可藉由將例行的添加劑如防污劑、塑化劑、塗膜消耗控制劑、顏料、溶劑等加到上述本發明的丙烯酸樹脂組成物及藉由混合機如球磨機、卵石磨機、輥磨機、砂磨機等將它們摻合一起而製得。當藉由習知技術將上述防污塗料塗佈於基材表面上及在周圍溫度或高溫下使其之溶劑蒸發掉，則該防污塗料形成一種乾膜。因爲本發明的丙烯酸樹脂具有至少一個至少一個以上通式（1)所表示的基及至少一個以上通式（2)所表示的基，故由含此丙烯酸樹脂的防污塗料所可獲得的塗膜係顯示長時間的穩定拋光速率且幾乎沒有發生裂紋，結果表現優良的長期防污性能；因此沒有由含有含三有機矽烷基樹脂的習知防污塗料所形成的塗膜之問題，例如習知的塗膜暴露於水中一段時間後會溶出進入水中或發生裂紋而喪失其防污性能及無法維持長期的防污性能。再者，因爲由本發明丙烯酸樹脂所可獲得的塗膜之曝露期間與塗膜之消耗厚度之 23 200301E63 間的關係大約線性的，故塗膜表現持續經時地穩定拋光速率，因此顯現優良的長期防污性能。爲此緣故，含本發明丙烯酸樹脂的防污塗料可有利地應用於船、魚網及其它水下構造。實行本發明的最佳模式以下實施例係爲本發明之更進一步說明而非用於限定本發明。在實施例中，除非另有指明，否則所有的份係重量份。樹脂淸漆的製備依照以下樹脂淸漆製造例1〜9來製備淸漆A〜I。表1中所示的單體係爲以下化合物。表1中亦顯示所製備的淸漆 A〜I之加登納（Gardner)黏度値（25t)。 EA :丙烯酸乙酯 CHMA :甲基丙烯酸環己酯 CHA :丙烯酸環己酯 M-90G:甲氧化聚乙二醇甲基丙烯酸酯 (NK Ester M-90G ; Shin-Nakamura 化學公司的產品） NBA :丙烯酸正丁酯 MMA :甲基丙烯酸甲酯 AA :丙烯酸 MAA :甲基丙烯酸 IIPSI :丙烯酸酯 TBSI :丙烯酸三丁基矽烷酯樹脂淸漆製浩例1 24 2ΰ030Π63 於設有攪拌器、冷凝器、溫度控制、氮氣入口管及滴液漏斗的四頸燒瓶內，加入64份二甲苯及16份正丁醇，並將溫度維持在l〇〇°C。於此溶液內，以等速逐滴添加表1 中所示式之單體成分（重量份）和3份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使混合物熟成30分鐘。然後，以等速逐滴添加16份二甲苯、4份正丁醇和0.2份過氧基-2-乙基己酸第三丁酯之混合物，歷 30分鐘。在完成逐滴添加後，使反應混合物熟成1.5小時〇所獲得者爲淸漆A，其具有50.2%的不揮發性部分，黏度爲23泊，且數量平均分子量爲7,000。所獲得的樹脂之酸値（不揮發性部分；以下亦適用）爲250。樹脂淸漆製造例2 在類似於樹脂淸漆製造例1中所用的反應容器內，加入72份二甲苯和18份正丁醇，及將加料維持在115°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和2份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使反應混合物熟成1小時。所獲得者爲淸漆B，其具有50.0%的不揮發性部分，黏度爲11泊，且數量平均分子量爲5,000。所獲得的樹脂之酸値爲130。樹脂淸漆製造例3 在類似於樹脂淸漆製造例1中所用的反應容器內，加入64份二甲苯和16份正丁醇，及將加料維持在110°C。於 25 200301E63 此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和3份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成1小時。所獲得者爲淸漆C，其具有49.5%的不揮發性部分，黏度爲7泊，且數量平均分子量爲6,500。所獲得的樹脂之酸値爲150。樹脂淸漆製造例4 在類似於樹脂淸漆製造例1中所用的反應容器內，加入64份二甲苯和16份正丁醇，及將加料維持在115°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和2份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後，以等速逐滴添加16份二甲苯、4份正丁醇和0.2份過氧基-The above pigments include extender pigments, such as precipitated barium, talc, clay, chalk, silica white, alumina white, bentonite, etc .; and color pigments such as titanium dioxide, zirconia, basic lead sulfate, tin oxide, carbon black, graphite , Red iron oxide, chrome yellow, peptide green, phthalocyanin blue, quinacridone and so on. These pigments may be used independently or in combination of two or more. The above solvents include hydrocarbons such as toluene, xylene, ethylbenzene, chloropentane, octane, heptane, cyclohexane, volatile oil, etc .; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and the like. 22 2ύϋ3〇1 £ 63 Ester, such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc .; ketones, such as ethyl isobutyl ketone , Methyl isobutyl ketone, etc .; and alcohols, such as n-butanol, propanol, and the like. These solvents may be used independently or in combination of two or more. As for other additives, there is no particular limitation. For example, mention may be made of monobasic organic acids, such as monobutyl phthalate, octyl succinate, etc., camphor, castor oil, etc .; water-binding agents, anti-flow agents, anti-overflow agents; anti-settling agents; and defoamers and many more. The antifouling paint according to the present invention can be added to the above-mentioned acrylic resin composition of the present invention by a conventional additive such as an antifouling agent, a plasticizer, a film consumption control agent, a pigment, a solvent, etc., and by a mixer, for example. Such as ball mills, pebble mills, roll mills, sand mills, etc., which are prepared by blending them together. When the above-mentioned antifouling coating is coated on the surface of a substrate by conventional techniques and its solvent is evaporated off at ambient or high temperature, the antifouling coating forms a dry film. Since the acrylic resin of the present invention has at least one group represented by the general formula (1) and at least one group represented by the general formula (2), the coating obtainable by the antifouling coating containing the acrylic resin The film shows a stable polishing rate for a long time and almost no cracks occur, resulting in excellent long-term antifouling performance; therefore, there is no problem with the coating film formed by the conventional antifouling coating containing triorganosilyl resin, such as conventional After being exposed to water for a period of time, the known coating film will dissolve into the water or crack and lose its antifouling performance and cannot maintain long-term antifouling performance. Furthermore, since the relationship between the exposure period of the coating film obtainable from the acrylic resin of the present invention and the thickness of the consumed film thickness of 23 200301E63 is approximately linear, the coating film performance continues to stabilize the polishing rate over time, thus exhibiting excellent long-term Antifouling performance. For this reason, the antifouling paint containing the acrylic resin of the present invention can be advantageously applied to ships, fishnets, and other underwater structures. Best Mode for Carrying Out the Invention The following examples are provided to further illustrate the invention and are not intended to limit the invention. In the examples, all parts are by weight unless otherwise specified. Preparation of Resin Varnishes Varnishes A to I were prepared according to the following Resin Varnish Production Examples 1 to 9. The single systems shown in Table 1 are the following compounds. Table 1 also shows the Gardner viscosity (25t) of the prepared lacquers A to I. EA: ethyl acrylate CHMA: cyclohexyl methacrylate CHA: cyclohexyl acrylate M-90G: methoxy polyethylene glycol methacrylate (NK Ester M-90G; product of Shin-Nakamura Chemical Co., Ltd.) NBA: N-butyl acrylate MMA: methyl methacrylate AA: acrylic acid MAA: methacrylic acid IIPSI: acrylate TBSI: tributylsilyl acrylate resin lacquer lacquer Example 1 24 2ΰ030Π63 There is a stirrer, condenser, temperature In a four-necked flask with a nitrogen inlet tube and a dropping funnel, 64 parts of xylene and 16 parts of n-butanol were added, and the temperature was maintained at 100 ° C. In this solution, a mixture of a monomer component (parts by weight) of the formula shown in Table 1 and 3 parts of peroxy-2-ethylhexanoic acid tributyl ester was added dropwise at a constant rate over 3 hours. After the dropwise addition is complete, the mixture is allowed to mature for 30 minutes. Then, a mixture of 16 parts of xylene, 4 parts of n-butanol and 0.2 parts of peroxy-2-ethylhexanoic acid tert-butyl ester was added dropwise at a constant speed over 30 minutes. After the dropwise addition was completed, the reaction mixture was aged for 1.5 hours. The obtained was lacquer A, which had a nonvolatile portion of 50.2%, a viscosity of 23 poise, and a number average molecular weight of 7,000. The obtained resin had a rhenium acid (nonvolatile fraction; the following also applies) of 250. Resin Varnish Production Example 2 In a reaction vessel similar to that used in Resin Varnish Production Example 1, 72 parts of xylene and 18 parts of n-butanol were charged, and the addition was maintained at 115 ° C. In this solution, a mixture of the monomer component (parts by weight) of the formula shown in Table 1 and 2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 3 hours. After completion of the dropwise addition, the reaction mixture was allowed to mature for 1 hour. The obtained was lacquer B, which had a nonvolatile portion of 50.0%, a viscosity of 11 poise, and a number average molecular weight of 5,000. The acid resistance of the obtained resin was 130. Resin Varnish Production Example 3 In a reaction vessel similar to that used in Resin Varnish Production Example 1, 64 parts of xylene and 16 parts of n-butanol were charged, and the addition was maintained at 110 ° C. In 25 200301E63, a mixture of the monomer component (parts by weight) of the formula shown in Table 1 and 3 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed into this solution for 3 hours. . After the dropwise addition is complete, the entire mixture is allowed to mature for 1 hour. The obtained was lacquer C, which had a non-volatile portion of 49.5%, a viscosity of 7 poise, and a number average molecular weight of 6,500. The acid fluorene of the obtained resin was 150. Resin Varnish Production Example 4 In a reaction vessel similar to that used in Resin Varnish Production Example 1, 64 parts of xylene and 16 parts of n-butanol were charged, and the addition was maintained at 115 ° C. In this solution, a mixture of the monomer component (parts by weight) of the formula shown in Table 1 and 2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, 16 parts of xylene, 4 parts of n-butanol and 0.2 parts of peroxy-

I 2-乙基己酸第三丁酯之混合物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成1.5小時。所獲得者爲淸漆D，其具有49.6%的不揮發性部分，黏度爲6泊，且數量平均分子量爲6,000。所獲得的樹脂之酸値爲70。樹脂淸漆製造例5 在類似於樹脂淸漆製造例1中所用的反應容器內，加入64份二甲苯和16份正丁醇，及將加料維持在105°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和2份偶氮雙異丁氰之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後，以等速逐滴添 26 0301E63 · 加16份二甲苯、4份正丁醇和0.2份偶氮雙異丁氰之混合 ' 物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成 1.5小時。所獲得者爲淸漆E，其具有49.9%的不揮發性部分，黏度爲10泊，且數量平均分子量爲6,500。所獲得的樹脂之酸値爲200。樹脂淸漆製浩例6 在類似於樹脂淸漆製造例1中所用的反應容器內，加 φ 入64份二甲苯和16份正丁醇，及將加料維持在115°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和2份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後，以等速逐滴添加16份二甲苯、4份正丁醇和0.2份過氧基-2-乙基己酸第三丁酯之混合物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成1.5小時。所獲得者爲淸漆F，其具有50.0%的不揮發性部分，黏 φ 度爲25泊，且數量平均分子量爲6,000。所獲得的樹脂之酸値爲130。樹脂淸漆製造例7 在類似於樹脂淸漆製造例1中所用的反應容器內，加入72份二甲苯和18份正丁醇，及將加料維持在105°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和3份偶氮雙異丁氰之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後，以等速逐滴添 27 0301E63 加8份二甲苯、2份正丁醇和0.2份偶氮雙異丁氰之混合物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成1.5 小時。所獲得者爲淸漆G，其具有50.8%的不揮發性部分，黏度爲4泊，且數量平均分子量爲6,000。所獲得的樹脂之酸値爲3 0。樹脂淸漆製浩例8 在類似於樹脂淸漆製造例1中所用的反應容器內，加入64份二甲苯和16份正丁醇，及將加料維持在115°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和3份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後，以等速逐滴添加16份二甲苯、4份正丁醇和0.2份過氧基-2-乙基己酸第三丁酯之混合物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成1.5小時。所獲得者爲淸漆Η，其具有49.7%的不揮發性部分，黏度爲9.5泊，且數量平均分子量爲6,500。所獲得的樹脂之酸値爲160。樹脂淸漆製浩例9 在類似於樹脂淸漆製造例1中所用的反應容器內，加入64份二甲苯和16份正丁醇，及將加料維持在100°C。於此溶液內，以等速逐滴添加表1中所示式之單體成分（重量份）和2份過氧基-2-乙基己酸第三丁酯之混合物，歷3小時。在完成逐滴添加後，使整個混合物熟成30分鐘。然後， 28 i “ b j 以等速逐滴添加16份二甲苯、4份正丁醇和0.2份過氧基-2-乙基己酸第三丁酯之混合物，歷30分鐘。在完成逐滴添加後，使反應混合物熟成1.5小時。所獲得者爲淸漆I，其具有60.0%的不揮發性部分，黏度爲7泊，且數量平均分子量爲8,000。 i “ b jMixture of I-ethylhexanoic acid tert-butyl ester over 30 minutes. After completion of the dropwise addition, the reaction mixture was allowed to mature for 1.5 hours. The obtained was lacquer D, which had a nonvolatile portion of 49.6%, a viscosity of 6 poise, and a number average molecular weight of 6,000. The acid fluorene of the obtained resin was 70. Resin Varnish Production Example 5 In a reaction vessel similar to that used in Resin Varnish Production Example 1, 64 parts of xylene and 16 parts of n-butanol were charged, and the addition was maintained at 105 ° C. In this solution, a mixture of a monomer component (parts by weight) of the formula shown in Table 1 and 2 parts of azobisisobutylcyanide was added dropwise at a constant speed for 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, add 26 0301E63 dropwise at a constant speed. Add a mixture of 16 parts of xylene, 4 parts of n-butanol, and 0.2 parts of azobisisobutylcyanide over 30 minutes. After completion of the dropwise addition, the reaction mixture was allowed to mature for 1.5 hours. The obtained was lacquer E, which had a non-volatile fraction of 49.9%, a viscosity of 10 poise, and a number average molecular weight of 6,500. The obtained resin had an acid hydrazone of 200. Example 6 made of resin varnish In a reaction vessel similar to that used in Production Example 1 of resin varnish, φ was charged with 64 parts of xylene and 16 parts of n-butanol, and the addition was maintained at 115 ° C. In this solution, a mixture of the monomer component (parts by weight) of the formula shown in Table 1 and 2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, a mixture of 16 parts of xylene, 4 parts of n-butanol, and 0.2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 30 minutes. After completion of the dropwise addition, the reaction mixture was allowed to mature for 1.5 hours. The obtained was lacquer F, which had a nonvolatile portion of 50.0%, a viscosity φ of 25 poise, and a number average molecular weight of 6,000. The acid resistance of the obtained resin was 130. Resin Varnish Production Example 7 In a reaction vessel similar to that used in Resin Varnish Production Example 1, 72 parts of xylene and 18 parts of n-butanol were charged, and the addition was maintained at 105 ° C. In this solution, a mixture of a monomer component (parts by weight) of the formula shown in Table 1 and 3 parts of azobisisobutylcyanide was added dropwise at a constant speed over 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, 27 0301E63 was added dropwise at a constant speed, and a mixture of 8 parts of xylene, 2 parts of n-butanol and 0.2 parts of azobisisobutylcyanide was added for 30 minutes. After the dropwise addition was completed, the reaction mixture was allowed to mature for 1.5 hours. The obtained was lacquer G, which had a non-volatile fraction of 50.8%, a viscosity of 4 poise, and a number average molecular weight of 6,000. The acid fluorene of the obtained resin was 30. Example 8 made of resin varnish In a reaction vessel similar to that used in Production Example 1 of resin varnish, 64 parts of xylene and 16 parts of n-butanol were charged, and the addition was maintained at 115 ° C. In this solution, a mixture of a monomer component (parts by weight) of the formula shown in Table 1 and 3 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, a mixture of 16 parts of xylene, 4 parts of n-butanol, and 0.2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 30 minutes. After completion of the dropwise addition, the reaction mixture was allowed to mature for 1.5 hours. The obtained was lacquer lacquer, which had a non-volatile fraction of 49.7%, a viscosity of 9.5 poise, and a number average molecular weight of 6,500. The acid resistance of the obtained resin was 160. Example 9 made of resin varnish In a reaction vessel similar to that used in Production Example 1 of resin varnish, 64 parts of xylene and 16 parts of n-butanol were charged, and the addition was maintained at 100 ° C. In this solution, a mixture of the monomer component (parts by weight) of the formula shown in Table 1 and 2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at a constant speed over 3 hours. After the dropwise addition is complete, the entire mixture is allowed to mature for 30 minutes. Then, a mixture of 16 parts of xylene, 4 parts of n-butanol, and 0.2 parts of peroxy-2-ethylhexanoic acid third butyl ester was added dropwise at 28 i "bj at a constant speed over 30 minutes. After the dropwise addition was completed Then, the reaction mixture was aged for 1.5 hours. The obtained was lacquer I, which had a nonvolatile portion of 60.0%, a viscosity of 7 poise, and a number average molecular weight of 8,000. I "bj

29 200301E63 I嗽樹脂淸漆製造例 ON HH 1 1 1 1 1 35.00 1 1 65.00 1 1 60.0 u-v 〇〇 ffi 16.30 15.00 15.00 20.00 1 卜 t-H r-H 10.27 12.26 1 1 160 49.7 v-w 卜〇 I 1 1 1 1 26.15 3.85 1 70.00 1 50.8 0-P VO 48.32 15.00 1 10.00 1 1 16.68 1 10.00 1 130 50.0 Z-Zl W 12.96 15.00 1 o o in 1 1 12.83 15.34 38.87 1 200 49.9 寸 Q 26.02 15.00 1 10.00 1 1 8.98 1 40.00 1 o 49.6 T-U ΓΟ U 1 1 25.00 20.00 5.70 10.00 19.30 I 1 20.00 150 49.5 U-V (N PQ 14.18 15.00 1 10.00 1 1 8.34 9.96 42.52 1 130 50.0 w-x T-H < 7.42 30.00 1 1 1 1 32.08 1 1 30.50 250 50.2 N 樹脂淸漆 EA CHMA CHA M-90G NBA MMA AA MAA TIPSI TBSI 酸値不揮發性部分（％) 加登納黏度（25°c) 單體 (重量份） οε29 200301E63 Manufacturing example of resin resin lacquer ON HH 1 1 1 1 1 35.00 1 1 65.00 1 1 60.0 uv 〇〇ffi 16.30 15.00 15.00 20.00 1 bH rH 10.27 12.26 1 1 160 49.7 vw b 1I 1 1 1 26.15 3.85 1 70.00 1 50.8 0-P VO 48.32 15.00 1 10.00 1 1 16.68 1 10.00 1 130 50.0 Z-Zl W 12.96 15.00 1 oo in 1 1 12.83 15.34 38.87 1 200 49.9 inch Q 26.02 15.00 1 10.00 1 1 8.98 1 40.00 1 o 49.6 TU ΓΟ U 1 1 25.00 20.00 5.70 10.00 19.30 I 1 20.00 150 49.5 UV (N PQ 14.18 15.00 1 10.00 1 1 8.34 9.96 42.52 1 130 50.0 wx TH < 7.42 30.00 1 1 1 1 32.08 1 1 30.50 250 50.2 N Resin lacquer EA CHMA CHA M-90G NBA MMA AA MAA TIPSI TBSI Acid non-volatile part (%) Gardner viscosity (25 ° c) monomer (parts by weight) ε

0301E63 丙烯酸樹脂淸漆的製備使用樹脂淸漆製造例1〜9中所獲得的淸漆A〜I，依照丙烯酸樹脂淸漆製造例1〜11來製備淸漆1〜11。丙烯酸樹脂淸漆製浩例1 於設有攪拌器、氮氣入口管、回流冷凝器、傾析器及溫度控制的四頸燒瓶內，加入100份淸漆A、48.9份醋酸鋅、78.1份氫化松香（酸値160)及60份二甲苯，及使溫度上升至回流溫度。去除醋酸、水和溶劑的流出混合物，及添加對應量的二甲苯-丁醇混合物，反應繼續進行18小時。藉由對流出的溶劑中之醋酸作定量，以測定反應的終點〇冷卻後，添加丁醇和二甲苯之混合物，藉以得到具有 55%不揮發性成分的淸漆1。丙烯酸樹脂淸漆製造例2 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆B、24.1份醋酸銅、40.6份氫化松香( 酸値160)及60份二甲苯，及使溫度上升至回流溫度。去除醋酸、水和溶劑的流出混合物，及添加對應量的二甲苯，反應繼續進行18小時。藉由對流出的溶劑中之醋酸作定量，以測定反應的終點。冷卻後，添加丁醇和二甲苯之混合物，藉以得到具有 50.2%不揮發性成分的淸漆2。丙烯酸樹脂淸漆製浩例3 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器 31 20ϋ301Ε63 內，加入100份淸漆C、27.8份醋酸銅及47.0份WW松香( 酸値160)，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有47.3%不揮發性成分的淸漆3。丙烯酸樹脂淸漆製浩例4 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆D、12.97份醋酸銅及21.88份氫化松香（酸値160)，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有51.3%不揮發性成分的淸漆4。丙烯酸樹脂淸漆製浩例5 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆E、39.1份醋酸鋅及62.5份WW松香（酸値160)，及另以相同於丙烯酸樹脂淸漆製造例1之方式來進行反應，而得到具有53.3%不揮發性成分的淸漆5。丙烯酸樹脂淸漆製造例6 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆F、24.09份醋酸銅及40.63份氫化松香（酸値160)，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有50.2%不揮發性成分的淸漆6。丙烯酸樹脂淸漆製浩例7 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆G、5.56份醋酸銅及9.38份氫化松香（酸値160)，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有60.2%不揮發性成分的淸漆7。丙烯酸樹脂淸漆製浩例8 32 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆D、37.06份醋酸銅及60.6份環烷酸 (NA-165，酸値165，大和油脂工業的產品），及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有 50.6%不揮發性成分的淸漆8。丙烯酸樹脂淸漆製浩例9 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆D、37.06份醋酸銅及15.0份三甲基乙酸，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有50.6%不揮發性成分的淸漆9。丙烯酸樹脂淸漆製造例10 在類似於丙烯酸樹脂淸漆製造例1中所用的反應容器內，加入100份淸漆Η、29.6份醋酸銅及12.6份三甲基乙酸，及另以相同於丙烯酸樹脂淸漆製造例2之方式來進行反應，而得到具有45.2%不揮發性成分的淸漆10。丙烯酸樹脂淸漆製造例11 使用樹脂淸漆製造例9中所獲得的淸漆I當作淸漆11 〇實施例1〜11和比較例1〜3 使用高速分散機（Disper)來分別混合丙烯酸樹脂淸漆製造例1〜11中所獲得的淸漆1〜11及表2中所示的其它成分，以製備塗料組成物，及依照以下評估方法來評估各組成物的長期防污性能及塗膜狀況。表3中顯示評估結果。表2 中所示的防污劑係爲以下化合物；丙烯酸樹脂係”Paraloid ϋ301Ε63 B-66”(Rohm & Hass公司的產品）；而防流淌劑係” Disparlon A 630-20X”(Kusumoto 化成的產品）。防污劑1 : ZPT(锍氧吡啶鋅）防污劑2 : CuPT(锍氧毗啶銅）防污劑3 :毗啶三苯基硼烷防污劑4 ·· 2-甲基硫基-4-第三丁基胺基-6-環丙基胺基-s-三畊防污劑5 : 4,5-二氯-2-正辛基-3(2H)異噻唑酮防污劑6 : N，N-二甲基-N’·苯基-(N-氟二氯甲基硫基）磺醯胺防污劑7 :硬脂醯胺-三苯基硼防污劑8 :月桂胺-三苯基硼0301E63 Preparation of acrylic resin varnishes Using Varnishes A to I obtained in Resin Varnishes Production Examples 1 to 9, varnishes 1 to 11 were prepared in accordance with Acrylic resin varnishes Production Examples 1 to 11. Example 1 made of acrylic resin varnish 1 In a four-necked flask equipped with a stirrer, nitrogen inlet tube, reflux condenser, decanter, and temperature control, 100 parts of varnish A, 48.9 parts of zinc acetate, and 78.1 parts of hydrogenated rosin were added. (Acid hydrazone 160) and 60 parts of xylene, and the temperature was raised to the reflux temperature. The effluent mixture of acetic acid, water and solvent was removed, and the corresponding amount of xylene-butanol mixture was added, and the reaction was continued for 18 hours. The end point of the reaction was determined by quantifying the acetic acid in the effluent solvent. After cooling, a mixture of butanol and xylene was added to obtain the varnish 1 having a non-volatile content of 55%. Acrylic resin varnish production example 2 In a reaction vessel similar to that used in acrylic resin varnish production example 1, 100 parts of varnish B, 24.1 parts of copper acetate, 40.6 parts of hydrogenated rosin (acid tincture 160), and 60 parts of xylene were charged. , And increase the temperature to reflux temperature. The effluent mixture of acetic acid, water and solvent was removed, and a corresponding amount of xylene was added, and the reaction was continued for 18 hours. The end point of the reaction was determined by quantifying the acetic acid in the effluent solvent. After cooling, a mixture of butanol and xylene was added to obtain a varnish 2 having a nonvolatile content of 50.2%. Example 3 made of acrylic resin lacquer In a reaction vessel 31 20ϋ301E63 similar to that used in Production Example 1 of acrylic resin lacquer, 100 parts of lacquer C, 27.8 parts of copper acetate, and 47.0 parts of WW rosin (acid 値 160) were added, and The reaction was carried out in the same manner as in Production Example 2 of acrylic resin varnish, and varnish 3 having 47.3% nonvolatile content was obtained. Example 4 made of acrylic resin varnish In a reaction vessel similar to that used in Production Example 1 of acrylic resin varnish, 100 parts of varnish D, 12.97 parts of copper acetate, and 21.88 parts of hydrogenated rosin (acid tincture 160) were added. The reaction was performed in the same manner as in the acrylic resin varnish production example 2, and a varnish 4 having 51.3% nonvolatile content was obtained. Example 5 made of acrylic resin varnish In a reaction vessel similar to that used in Production Example 1 of acrylic resin varnish, 100 parts of varnish E, 39.1 parts of zinc acetate, and 62.5 parts of WW rosin (acid tantalum 160) were added, The reaction was carried out in the same manner as in Production Example 1 of acrylic resin varnish, and varnish 5 having a nonvolatile content of 53.3% was obtained. Acrylic resin varnish production example 6 In a reaction vessel similar to that used in acrylic resin varnish production example 1, 100 parts of varnish F, 24.09 parts of copper acetate, and 40.63 parts of hydrogenated rosin (acid tincture 160) were added. The reaction was carried out in the same manner as in Acrylic Resin Varnish Production Example 2 to obtain Varnish 6 having a nonvolatile content of 50.2%. Example 7 made of acrylic resin varnish In a reaction vessel similar to that used in Production Example 1 of acrylic resin varnish, 100 parts of varnish G, 5.56 parts of copper acetate, and 9.38 parts of hydrogenated rosin (acid tantalum 160) were added. The reaction was carried out in the same manner as in Production Example 2 of acrylic resin varnish, and varnish 7 having 60.2% nonvolatile content was obtained. Example 8 of acrylic resin varnish 8 32 In a reaction vessel similar to that used in Production Example 1 of acrylic resin varnish, 100 parts of varnish D, 37.06 parts of copper acetate, and 60.6 parts of naphthenic acid (NA-165, acid 165, a product of Yamato Grease Industry Co., Ltd.), and reacted in the same manner as in Production Example 2 of acrylic resin varnish, to obtain varnish 8 having a nonvolatile content of 50.6%. Example 9 made of acrylic resin lacquer In a reaction vessel similar to that used in Production Example 1 of acrylic resin lacquer, 100 parts of lacquer D, 37.06 parts of copper acetate and 15.0 parts of trimethylacetic acid were added, and the same as acrylic acid was used. The resin varnish was produced in the same manner as in Production Example 2 to obtain varnish 9 having a nonvolatile content of 50.6%. Acrylic resin varnish production example 10 In a reaction vessel similar to that used in acrylic resin varnish production example 1, 100 parts of varnish, 29.6 parts of copper acetate, and 12.6 parts of trimethylacetic acid were added, and the same as acrylic resin was used. The varnish was produced in the same manner as in Production Example 2 to obtain varnish 10 having 45.2% nonvolatile content. Acrylic resin varnish production example 11 The varnish I obtained in resin varnish production example 9 was used as varnish 11 〇 Examples 1 to 11 and Comparative Examples 1 to 3 The acrylic resin was mixed separately using a high-speed disperser (Disper). The varnishes 1 to 11 obtained in the varnish production examples 1 to 11 and other ingredients shown in Table 2 were used to prepare coating compositions, and the long-term antifouling performance and coating film of each composition were evaluated according to the following evaluation methods. situation. The evaluation results are shown in Table 3. The antifouling agents shown in Table 2 are the following compounds; acrylic resins “Paraloid 301301 63 B-66” (products of Rohm &Hass); and anti-flow agents “Disparlon A 630-20X” (made by Kusumoto) product). Antifouling agent 1: ZPT (zinc pyridinium zinc) Antifouling agent 2: CuPT (coppoxopyridine copper) Antifouling agent 3: Pyridyltriphenylborane antifouling agent 4 ·· 2-methylthio- 4-Third-butylamino-6-cyclopropylamino-s-three-field antifouling agent 5: 4,5-dichloro-2-n-octyl-3 (2H) isothiazolone antifouling agent 6 : N, N-dimethyl-N '· phenyl- (N-fluorodichloromethylthio) sulfonamide antifouling agent 7: stearylamine-triphenylboron antifouling agent 8: laurylamine -Triphenylboron

34 20ϋ301£63 表2 單位：重量份實施例比較例 1 2 3 4 5 6 7 8 9 10 11 1 2 3 淸漆1 36 淸漆2 - 40 32 淸漆3 42 淸漆4 31 31 淸漆5 38 淸漆6 32 淸漆7 33 淸漆8 32 淸漆9 33 淸漆10 35 淸漆11 34 27 氧化低價銅 - 一 — 35 - 35 35 35 35 35 35 35 - 35 鋅白 25 25 25 5 25 5 5 5 5 5 5 5 25 5 紅氧化鐵 2 2 2 2 2 2 2 2 2 2 2 2 2 2 防污劑i — — — 4 — — - 4 2 - - 4 4 — 防污劑2 4 4 4 - 1 2 1 — 2 4 1 - — 4 防污劑3 2 — 3 - 4 防污劑4 2 1 1 - — 1 1 — - - 1 - - — 防污劑5 1 — 一 — - — 1 — - - 1 - 1 — 防污劑6 一 2 防污劑7 - 1 2 — 防污劑8 3 2 - 氯化石蠟 2 4 4 4 2 4 4 2 4 4 4 2 4 - 樹膠松香 4 木松香 - 4 4 氫化樹膠松香 4 松香酯 2 2 2 樹膠松香_鋅 4 4 - 丙烯酸樹脂 5 5 5 — 5 — - 2 - — - 2 5 - 防流淌劑 2 2 2 2 2 2 2 2 2 2 2 2 2 2 甲基異丁基酮 - 3 3 3 - 3 - 3 — 3 — 3 3 3 二甲苯 15 7 5 12 17 11 14 13 16 14 14 6 12 22 總共 100 100 100 100 100 100 100 100 100 100 100 100 100 10034 20ϋ301 £ 63 Table 2 Unit: parts by weight Example Comparative Example 1 2 3 4 5 6 7 8 9 10 11 1 2 3 Lacquer 1 36 Lacquer 2-40 32 Lacquer 3 42 Lacquer 4 31 31 Lacquer 5 38 lacquer 6 32 lacquer 7 33 lacquer 8 32 lacquer 9 33 lacquer 10 35 lacquer 11 34 27 low-cost copper oxide-one-35-35 35 35 35 35 35 35 35-35 zinc white 25 25 25 5 25 5 5 5 5 5 5 5 25 5 Red iron oxide 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Antifouling agent i — — — 4 — —-4 2--4 4 — Antifouling agent 2 4 4 4-1 2 1 — 2 4 1-— 4 Antifouling agent 3 2 — 3-4 Antifouling agent 4 2 1 1-— 1 1 —--1--— Antifouling agent 5 1 — One —-— 1 —--1-1 — antifouling agent 6-2 antifouling agent 7-1 2 — antifouling agent 8 3 2-chlorinated paraffin 2 4 4 4 2 4 4 2 4 4 4 2 4-gum rosin 4 wood Rosin-4 4 Hydrogenated Gum Rosin 4 Rosin Ester 2 2 2 Tree Rosin_zinc 4 4-Acrylic resin 5 5 5 — 5 —-2-—-2 5-Anti-flowing agent 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Methyl isobutyl ketone-3 3 3- 3-3 — 3 — 3 3 3 Xylene 15 7 5 12 17 11 14 13 16 14 14 6 12 22 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100

<評估〉拋光速率在一經防銹塗料所預塗覆的噴淨片上，以300μιη的乾塗膜厚度塗佈上述各塗料組成物，及讓其在室中被乾燥兩夜，以製備一種試樣。使此試樣附著直徑750mm且長度 35 200301263 l，200mm的圓筒之側表面，及在海水中以15節的周邊速率連續轉動24個月。在三個月的間隔，測量試樣的塗膜消耗 (μιη，總共）。塗膜狀況在6個月暴露於上述條件下後，目視觀察試樣以評估塗膜的狀況。結果示於表3中。長期防污性能在塗膜的上述觀察後，在日本岡山縣玉野市的日本塗料公司之沿海（Coastal)硏究實驗室，使用實驗筏使試樣接受海洋生物沈積試驗。結果示於表3中。在表3中，月數代表由筏的浸漬持續時間，而數値代表相對於塗膜面積而言所沈積的生物之百分率。< Evaluation> A polishing rate was applied to a spray sheet pre-coated with an anti-rust coating, and each of the above coating compositions was coated at a dry film thickness of 300 μm, and allowed to dry in a room for two nights to prepare a test specimen. kind. This sample was attached to the side surface of a cylinder with a diameter of 750 mm and a length of 35 200301263 l, 200 mm, and continuously rotated in seawater at a peripheral rate of 15 knots for 24 months. At three-month intervals, the coating film consumption of the samples (μιη, total) was measured. Coating film condition After 6 months of exposure to the above conditions, the sample was visually observed to evaluate the condition of the coating film. The results are shown in Table 3. Long-term antifouling performance After the above observations of the coating film, the samples were subjected to marine biodeposition tests at the Coastal Research Laboratory of Japan Coatings Co., Ltd. in Tamano, Okayama Prefecture, Japan. The results are shown in Table 3. In Table 3, the months represent the duration of immersion by the raft, and the numbers represent the percentage of organisms deposited relative to the area of the coating film.

36 200301363 比較例 m Ο ο 00 m f·—Η Ό τ-Η 〇\ r-H m (N (Ν o ο ο ο ο r-H ο ο r-H 健全 (N Ο ο m 寸 τ-Η Ο νπ r-H 笑 (Ν 1 1 o ο ο ο ο ο ο τ··Η 健全 Η ο νο (Ν Τ—< 00 寸 τ-Η § τ-Η 00 r*H CN r-H τ-Η o ο ο ο ο ν-Η 裂紋實施例 t—< ο »〇卜 <Ν <Ν ΓΟ 艺 ν〇 m 00 m o ο ο ο ο 健全 Ο ο 00 Ο Ο Τ-Η m (Ν ^Η v〇 τ-Η o ο ο ο ο ο ! 健全〇\ ο 卜 S 芝 (Ν (Ν νο rn ^T) 00 o ο ο ο ο ο 健全1 00 ο ro 00 VO Ον Ον (Ν 1—( 00 寸 τ-Η ΙΟ VD f—Η 00 00 rH o ο ο ο ο ο 健全卜 ο ο i-H vr> (Ν $ Ο m νο tn 卜 S 00 ON o ο ο ο ο ο 1 健全 νο ο (Ν ΓΠ 卜 00 00 卜 (Ν Ον 00 o ^-H s τ-Η o ο ο ο ο ο 健全 ο (Ν m 00 ro VO ο 00 Ο 〇\ (N 1—H Os (N o ο ο ο ο ο 健全寸 ο m fN 00 ν〇 Ό 0\ m <Ν τ-Η 寸 r-H s l-H 00 r-H o ο ο ο ο ο 健全 j cn ο ο m (Ν ο o o T-H τ-Η o ο ο ο ο ο 健全 (N ο 00 ο ίΝ 寸卜 m 〇\ ro r-H r-H 芝 r-H tn f—* o ο ο ο ο ο 健全 τ-Η ο ν〇 m 00 (Ν Ο τ-Η 芝 CN τ-Η O r-H o ο ο ο ο ο 1 健全〇個月 3個月 6個月 9個月 1 12個月 15個月 18個月 21個月 24個月 3個月 6個月 9個月 12個月 18個月 24個月塗膜狀況惩？ m 5 劍長期防污性能36 200301363 Comparative example m Ο ο 00 mf · —Η Ό τ-Η 〇 \ rH m (N (Ν o ο ο ο rH ο ο rH sound (N Ο ο m inch τ-Η Ο νπ rH laughs (Ν 1 1 o ο ο ο ο ο τ ·· Η sound Η ο νο (Ν Τ— & 00 inch τ-Η § τ-Η 00 r * H CN rH τ-Η o ο ο ο ν-Η crack implementation Example t— < ο »〇卜 < N < Ν ΓΟ art ν〇m 00 mo ο ο ο ο sound ο ο ο 00 Ο Ο Τ-Η m (Ν ^ 〇 v〇τ-Η o ο ο ο ο ο! Sound 〇 \ ο Bu S Zhi (N (Ν νο rn ^ T) 00 o ο ο ο ο ο Sound 1 00 ο ro 00 VO Ον Ον (Ν 1— (00 inch τ-Η ΙΟ VD f-Η 00 00 rH o ο ο ο ο ο sound ο ο iH vr > (N $ Ο m νο tn S 00 ON o ο ο ο ο ο 1 sound νο ο (Ν ΓΠ 卜 00 00 (Ν Ον 00 o ^- H s τ-Η o ο ο ο ο ο sound ο (Ν m 00 ro VO ο 00 〇〇 \ (N 1—H Os (N o ο ο ο ο ο ο sound inch) m fN 00 ν〇Ό 0 \ m < Ν τ-Η inch rH s lH 00 rH o ο ο ο ο ο sound j cn ο ο m (Ν ο oo TH τ-Η o ο ο ο ο ο ο (N ο 00 ο ίΝ inch m 〇 \ ro rH rH zhi rH tn f— * o ο ο ο ο ο sound τ-Η ο ν〇m 00 (Ν Ο τ-Η ΗCN τ-Η O rH o ο ο ο ο ο 1 sound 0 months 3 months 6 months 9 months 1 12 months 15 months 18 months 21 months 24 months 3 months 6 months 9 months 12 months 18 months 24 How long is the coating film condition? M 5 Long-term antifouling performance

PiPi

200301263 由表3中可知，依實施例1〜l〇的各塗料保持長時間的穩定拋光速率且表現長期防污性能和良好的塗膜狀況。依實施例11的塗料在24個月後顯示輕微的污穢’但是塗膜狀況仍健全。由依比較例1〜3的塗料所獲得的塗膜係略微被消耗或在某一期間後不再被消耗或頗過度地被消耗，而在長期防污性能與塗膜狀況之間不能獲得和諧一致。200301263 As can be seen from Table 3, each of the coating materials according to Examples 1 to 10 maintained a stable polishing rate for a long time and exhibited long-term antifouling performance and good coating film conditions. The coating according to Example 11 showed slight staining after 24 months' but the condition of the coating film was still sound. The coating film obtained from the coating materials according to Comparative Examples 1 to 3 was slightly consumed or was no longer consumed or was consumed excessively after a certain period of time, and there was no harmony between the long-term antifouling performance and the condition of the coating film. .

3838

Claims

2ϋ0301 ^ 63 Patent application scope 1. An acrylic resin having at least one group represented by the following general formula: 0 R1 II I 2 t, —C—0—Si—R2 (1) R3 (wherein R1 , R2 and R3 are the same or different and each represent a hydrocarbon residue of 1 to 20 carbon atoms) in its side chain and additionally at least one of which is represented by the following general formula (2): 0 — (X) — C — ο —M—A (2): (where X is a group represented by: ΐ OHC I ο

η is equal to 0 or 1; Y represents a hydrocarbon residue; M represents a divalent metal; and A represents a monovalent organic acid residue) in its side chain. 2. An acrylic resin, characterized in that it can be obtained from the following steps: (A) step, comprising polymerizing 3 to 50% by weight of a polymerizable unsaturated organic acid, 90 to 5% by weight represented by the following general formula (3) Triorganosilyl (meth) acrylate: 39 (3) (3) 200301E63 Z 0 R4 H2C—C—C—0—Si— (where Z represents a hydrogen atom or a methyl group; R4, R5, and R6 are the same or different And each represents a hydrocarbon residue of 1 to 20 carbon atoms) and one or more other copolymerizable unsaturated monomers, and step (B) includes the resin, the metal compound and the monovalent obtained in the above step (A) The acid reacts. 3. The acrylic resin as claimed in claim 1 or 2, wherein the monobasic acid is a monobasic cyclic organic acid. 4. If the chloromer acid resin of the scope of application for patents No. 1, 2 or 3, at least one member of the monobasic acid is selected from the group consisting of rosin, hydrogenated rosin, disproportionated rosin, naphthenic acid, rosin acid, hydrogenated rosin acid, and dehydroabietic acid. Group of people. 5. For example, an acrylic resin in the scope of claims 1, 3 or 4, wherein in the general formula (1), R1, R2 and R3 each represent an isopropyl group. 6. For example, an acrylic resin in the scope of claims 2, 3 or 4, wherein in the general formula (3), R4, R5 and R6 each represent an isopropyl group. 7. An antifouling coating, including acrylic resins such as those in the scope of patent applications 1, 2, 3, 4, 5, or 6. Lu, (1), the designated representative figure in this case is: None. (2), the component representative symbols in this representative figure are simply explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention ::